Method of processing a surface of group iii nitride crystal and group iii nitride crystal substrate

ABSTRACT

There is provided a method of processing a surface of a group III nitride crystal, that includes the steps of: polishing a surface of a group III nitride crystal with a polishing slurry containing abrasive grains; and thereafter polishing the surface of the group III nitride crystal with a polishing liquid at least once, and each step of polishing with the polishing liquid employs a basic polishing liquid or an acidic polishing liquid as the polishing liquid. The step of polishing with the basic or acidic polishing liquid allows removal of impurity such as abrasive grains remaining on the surface of the group III nitride crystal after it is polished with the slurry containing the abrasive grains.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a method of processing a surface ofgroup III nitride crystal used for a substrate or the like of a lightemitting element, an electronic element, a semiconductor sensor and asimilar semiconductor device, and a group III nitride crystal substrateobtained by such method.

2. Description of the Background Art

Group III nitride crystal is significantly useful as a material forforming a substrate of a light emitting element, an electronic element,a semiconductor sensor and a similar semiconductor device. Group IIInitride crystal as referred to herein indicates a crystal formed of agroup III element and nitrogen, such as Al_(x)Ga_(y)In_(1-x-y)N crystalor the like, wherein 0≦x, 0≦y, and x+y≦1.

A group III nitride crystal substrate used as a substrate of asemiconductor device is obtained by working a perimeter of a group IIInitride crystal to have a geometry, then slicing it to have apredetermined thickness, and polishing its surface to be flat.

As the group III nitride crystal has a chemically stable surface, thesurface is mechanically or chemically mechanically polished with aslurry containing a abrasive grains. For example, U.S. Pat. No.6,488,767 discloses using a slurry containing abrasive grains of SiO₂ orAl₂O₃ to chemically mechanically polish a wafer ofAl_(x)Ga_(y)In_(1-x-y)N, wherein 0≦x, 0≦y, and x+y<1.

Consequently after the group III nitride crystal has been polished withthe slurry containing the abrasive grains it has a surface with theslurry containing the abrasive grains, residues resulting frompolishing, and other impurities remaining thereon. Of such impurities,the liquid of the slurry is removed typically by polishing or washingwith pure water. Simply polishing or washing with pure water, however,cannot sufficiently remove the abrasive grains, residues resulting frompolishing, and the like remaining on the surface of the group IIInitride crystal.

Accordingly, U.S. Pat. No. 6,399,500 proposes polishing with a basicpolishing liquid that does not contain abrasive grains, and thereafterpolishing with pure water.

SUMMARY OF THE INVENTION

U.S. Pat. No. 6,399,500, however, employs a basic component of NaOH,KOH, or the like. As such, ions of Na, K or a similar alkaline metalelement readily remain on a surface of a group III nitride crystal.

Furthermore, if a slurry used in polishing contains abrasive grainsother than SiO₂ and Al₂O₃, such as CeO₂, Fe₂O₃, Fe₃O₄, SnO₂, Cr₂O₃, andthe like, a basic polishing liquid and pure water cannot sufficientlyremove them.

The present invention contemplates a method of processing a surface of agroup III nitride crystal, that can remove abrasive grains or similarimpurities remaining on the surface of the group III nitride crystalafter it has been polished with a slurry containing the abrasive grains.

The present invention is a method of processing a surface of a group IIInitride crystal, that includes the steps of polishing a surface of agroup III nitride crystal with a polishing slurry containing abrasivegrains; and thereafter polishing the surface of the group III nitridecrystal with a polishing liquid at least once. Each step of polishingwith the polishing liquid employs one of a basic polishing liquid and anacidic polishing liquid as the polishing liquid. The basic polishingliquid contains at least one type selected from the group consisting ofa base having at least any of C, O, H and N as a constituent element, asalt thereof and an oxidizer having at least any of C, O, H and N as aconstituent element and has a pH of at least 8.5 and at most 14, and ifthe pH is represented by a value x and the basic polishing liquid has anoxidation reduction potential represented by a value y represented inmV, values x and y satisfy the following expression:

y>−50x+800  (i), and

the acidic polishing liquid contains at least one type selected from thegroup consisting of an acid having at least any of C, O, H and N as aconstituent element, a salt thereof and an oxidizer having at least anyof C, O, H and N as a constituent element and has a pH of at least 1.5and at most 6, and if the pH is represented by a value x and the acidicpolishing liquid has an oxidation reduction potential represented by avalue y represented in mV, values x and y satisfy the followingexpression:

y>−50x+800  (i).

Furthermore in the present method of processing a surface of a group IIInitride crystal the basic polishing liquid can further include achelate. Furthermore the steps of polishing with the polishing liquidcan include the steps of polishing with the basic polishing liquid andthereafter polishing with the acidic polishing liquid. Furthermore thesteps of polishing with the polishing liquid can include the steps ofpolishing with the acidic polishing liquid and thereafter polishing withthe basic polishing liquid.

Furthermore the present invention is a group III nitride crystalsubstrate obtained by the aforementioned method of processing a surfaceof a group III nitride crystal.

The present invention can thus provide a method of processing a surfaceof a group III nitride crystal, that can remove impurity such asabrasive grains remaining on the surface of the group III nitridecrystal after it is polished with a slurry containing the abrasivegrains.

The foregoing and other objects, features, aspects and advantages of thepresent invention will become more apparent from the following detaileddescription of the present invention when taken in conjunction with theaccompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic cross section for illustrating the step ofpolishing with a polishing slurry containing abrasive grains in a methodof processing a surface of a group III nitride crystal in accordancewith the present invention.

FIG. 2 is a schematic cross section for illustrating the step ofpolishing with a polishing liquid in a method of processing a surface ofa group III nitride crystal in accordance with the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS First Embodiment

The present invention provides a method of processing a surface of agroup III nitride crystal in one embodiment with reference to FIGS. 1and 2 including the step of polishing a surface of a group III nitridecrystal 1 with a polishing liquid 27 at least once after polishing thesurface with a polishing slurry 17 containing abrasive grains 16, andeach step of polishing with polishing liquid 27 employs a basicpolishing liquid or an acidic polishing liquid as polishing liquid 27.

Herein the basic polishing liquid contains at least one type selectedfrom the group consisting of a base having at least any of C, O, H and Nas a constituent element, a salt thereof and an oxidizer and has a pH ofat least 8.5 and at most 14, and if the pH is represented by a value xand the polishing liquid has an oxidation reduction potential (ORP)represented by a value y represented in mV, values x and y satisfy thefollowing expression:

y>−50x+800  (i).

Furthermore, the acidic polishing liquid contains at least one typeselected from the group consisting of an acid having at least any of C,O, H and N as a constituent element, a salt thereof and an oxidizer andhas a pH of at least 1.5 and at most 6, and if the pH is represented bya value x and the polishing liquid has an ORP represented by a value yrepresented in mV, values x and y satisfy the following expression:

y>−50x+800  (i)

Herein, an ORP indicates an energy level (or potential) determined byequilibrium between an oxidant and a reducer coexisting in a solution.An ORP obtained by measurement is a value for a reference electrode. Fordifferent types of reference electrodes, the same solution's measuredvalue apparently varies. In general academic articles and the like, anormal hydrogen electrode (NHE) is often used as the referenceelectrode. In the present application an ORP is indicated as a valueprovided such that the normal hydrogen electrode (NHE) serves as thereference electrode.

In such method of processing a surface of a group III nitride crystal,after group III nitride crystal 1 has a surface polished with polishingslurry 17 containing abrasive grains 16, the above described basic oracidic polishing liquid can be used to polish the surface at least onceto effectively remove the abrasive grains or similar impuritiesremaining on the surface of the group III nitride crystal after it ispolished with the slurry containing the abrasive grains.

Polishing with a polishing slurry containing abrasive grains, asreferred to in the present embodiment, indicates mechanically orchemically mechanically polishing a surface of group III nitride crystal1 with a polishing slurry containing abrasive grains. For example, withreference to FIG. 1, a polishing pad 18 fixed on a surface plate 15 isrotated around an axis of rotation 15 c, while a polishing slurry 17 isfed through a polishing slurry feeding port 19 onto polishing pad 18,and on a crystal holder 11 fixing group III nitride crystal 1 a weight14 is placed and rotated around an axis of rotation 11 c of the holderto press group III nitride crystal 1 against polishing pad 18 tomechanically or chemically mechanically polish the surface of group IIInitride crystal 1.

Abrasive grains 16 contained in polishing slurry 17 may be any abrasivegrains that can polish the surface of the group III nitride crystal, andcan be formed of material such as SiO₂, Al₂O₃, CeO₂, Fe₂O₃, Fe₃O₄, SnO₂,Cr₂O₃. Abrasive grains 16 may be a mixture of two or more types ofmaterials selected from the above indicated materials or a complexcompound thereof. If abrasive grains formed of two or more differenttypes of materials are used, high hardness abrasive grains higher inhardness than the group III nitride crystal and low hardness abrasivegrains lower in hardness than the group III nitride crystal arepreferably used to enhance the surface of the crystal in smoothness andpolish it faster. The high hardness abrasive grains can be formed forexample of Al₂O₃, Cr₂O₃. The low hardness abrasive grains can be formedfor example of SiO₂, CeO₂, Fe₂O₃, Fe₃O₄, SnO₂. The group III nitridecrystal and the abrasive grains are compared in hardness by bringing theformer and the latter into contact with each other, and one that hasbeen scratched is determined as being lower in hardness. If both arescratched, they are determined as being equal in hardness.

For polishing slurry 17, any medium may be used. Preferably, however,water is used. Furthermore, to provide an enhanced chemical polishingeffect, preferably, polishing slurry 17 is acidic with a pH of at most 6or basic with a pH of at least 8 and/or if the pH is represented by avalue x and the slurry has an ORP represented by a value y representedin mV then the following expression:

y>−50x+1000  (ii)

is satisfied. Accordingly, preferably, polishing slurry 17 contains atleast one type selected from the group consisting of an acid and a saltthereof, a base and a salt thereof, and an oxidizer.

Herein, the acid and the salt thereof can include nitric acid, carbonicacid, hydrochloric acid, sulfuric acid, phosphoric acid and likeinorganic acids, formic acid, acetic acid, citric acid, malic acid,tartaric acid, succinic acid, phthalic acid, fumaric acid, and likeorganic acids, and a salt thereof. The base and the salt thereof caninclude NH₄OH, amine, NaOH, KOH, and a salt thereof. The oxidizer caninclude nitric acid, oxygenated water, ozone as well as chlorinatedisocyanuric acid, chlorinated isocyanurate, permanganate, thiosulfate,persulfate and the like. Note that preferably, polishing slurry 17contains the acid and the salt thereof, the base and the salt thereof,and the oxidizer that have at least any of C, O, H and N as aconstituent element to facilitate removing impurities.

Polishing with a polishing liquid, as referred to in the presentembodiment, indicates mainly chemically polishing a surface of group IIInitride crystal 1 with a polishing liquid which does not containabrasive grains. For example, with reference to FIG. 2, a polishing pad28 fixed on a surface plate 25 is rotated around an axis of rotation 25c, while a polishing liquid 27 is fed through a polishing liquid feedingport 29 onto polishing pad 28, and on a crystal holder 21 fixing groupIII nitride crystal 1 a weight 24 is placed and rotated around an axisof rotation 21 c of the holder to press group III nitride crystal 1against polishing pad 28 to remove impurities such as abrasive grainsremaining on the surface of group III nitride crystal 1 after it ispolished with slurry. Note that the impurities include the abrasivegrains as well as the slurry, Na, Cu, Zn and similar metallic impuritiescontained in the slurry, and residues that result from polishing andderive from the polishing pad and/or the group III nitride crystal.

In the present embodiment the step of polishing with the polishingliquid is performed at least once. Performing the step of polishing withthe polishing liquid more than once can remove more impurities on thesurface of the group III nitride crystal. Note that for the polishingliquid any medium may be used, although water is preferably used to moreeffectively remove impurities.

In the present embodiment each step of polishing with the polishingliquid employs a basic polishing liquid or an acidic polishing liquid asthe polishing liquid. The basic or acidic polishing liquid can be used,depending on the type of abrasive grains used in the step of polishingwith a polishing slurry, to more effectively remove impurities includingthe abrasive grains.

If the step of polishing with a polishing slurry is performed withabrasive grains containing SiO₂, Al₂O₃ or the like as a material, thebasic polishing liquid is preferably used, since SiO₂, Al₂O₃ and thelike are readily soluble in basic, aqueous liquid. Hereinafter amaterial, such as SiO₂, Al₂O₃, readily soluble in the basic polishingliquid will be referred to as a base soluble material.

Such basic polishing liquid contains at least one type selected from thegroup consisting of a base having at least any of C, O, H and N as aconstituent element, a salt thereof and an oxidizer and has a pH of atleast 8.5 and at most 14, and if the pH is represented by a value x andthe polishing liquid has an ORP represented by a value y represented inmV, values x and y satisfy the following expression:

y>−50x+800  (i).

If the basic polishing liquid is a weakly basic polishing liquid havinga pH smaller than 8.5 or y≦50x+800 it removes impurities lesseffectively. Furthermore, the base, the salt thereof and the oxidizerthat have at least any of C, O, H and N as a constituent element, i.e.,exclude an element other than C, O, H and N, such as Na, K and the like,as an element can contribute to reduced impurities deriving from thepolishing liquid remaining on the surface of the group III nitridecrystal.

The base having at least any of C, O, H and N as a constituent elementand a salt thereof can include trimethyl ammonium oxide and similar,quaternary ammonium salts, NH₄OH, amines, and the like. The oxidizerhaving at least any of C, O, H and N as a constituent element caninclude nitric acid, oxygenated water, ozone, and the like.

If the step of polishing with the polishing slurry is performed withabrasive grains formed of material such as CeO₂, Fe₂O₃, Fe₃O₄, SnO₂,Cr₂O₃, the acidic polishing liquid is preferably used, since CeO₂,Fe₂O₃, Fe₃O₄, SnO₂, Cr₂O₃, and the like are readily soluble in acidic,aqueous liquid. Hereinafter a material, such as CeO₂, Fe₂O₃, Fe₃O₄,SnO₂, Cr₂O₃, readily soluble in the acidic polishing liquid will bereferred to as an acid soluble material.

Such acidic polishing liquid contains at least one type selected fromthe group consisting of an acid having at least any of C, O, H and N asa constituent element, a salt thereof and an oxidizer and has a pH of atleast 1.5 and at most 6, and if the pH is represented by a value x andthe polishing liquid has an ORP represented by a value y represented inmV, values x and y satisfy the following expression:

y>−50x+800  (i).

If the acidic polishing liquid is a weakly acidic polishing liquidhaving a pH larger than 6 or y≦50x+800 it removes impurities lesseffectively. Furthermore, the acid, the salt thereof and the oxidizerthat have at least any of C, O, H and N as a constituent element, i.e.,exclude an element other than C, O, H and N, such as S, P, Na, K and thelike, as an element can contribute to reduced impurities deriving fromthe polishing liquid remaining on the surface of the group III nitridecrystal.

Herein the acid having at least any of C, O, H and N as a constituentelement and the salt thereof can include nitric acid and like inorganicacids, formic acid, acetic acid, citric acid, malic acid, tartaric acid,succinic acid, phthalic acid, fumaric acid, and like organic acids, anda salt thereof. The oxidizer having at least any of C, O, H and N as aconstituent element can include nitric acid, oxygenated water, ozone andthe like.

Thus the basic and acidic polishing liquids contain a base and a saltthereof, an acid and a salt thereof, and an oxidizer that all contain atleast any of C, O, H and N as a constituent element. Such feature canreduce residual impurities deriving from the polishing liquid. Herein inorder to enhance the polishing liquid in ORP to further reduceimpurities remaining on the surface of the group III nitride crystal thebasic and acidic polishing liquids preferably contain an oxidizer havingat least any of C, O, H and N as a constituent element. Furthermore, thebasic and acidic polishing liquids both satisfy expression (1). Suchfeature can enhance the effect of removing impurities on the surface ofthe group III nitride crystal.

Furthermore in the present embodiment the above described basicpolishing liquid preferably contains a chelate to effectively removeimpurities, metallic ions in particular, remaining on the surface of thegroup III nitride crystal after it is polished with a slurry. Suchchelate is not particularly limited to any specific chelate. Preferably,however, ethylene diamine tetra acetic acid (EDTA), methylene sulfonicacid, ethylenediaminedi(orthohydroxyphenylacetic) acid (EDDHA), and aderivative thereof are preferably used as they are significantly capableof capturing metallic ions.

Second Embodiment

The present invention provides the method of processing a surface of agroup III nitride crystal in another embodiment with reference to FIGS.1 and 2 including the step of polishing a surface of group III nitridecrystal 1 with polishing liquid 27 at least once after polishing thesurface with polishing slurry 17 containing abrasive grains 16, and thestep of polishing with polishing liquid 27 includes the step ofpolishing with a basic polishing liquid and polishing with an acidicpolishing liquid. Herein the basic and acidic polishing liquids arethose described in the first embodiment.

Polishing with the basic polishing liquid can effectively removeimpurities including a base soluble material such as SiO₂, Al₂O₃ and thelike, and polishing with the acidic polishing liquid can effectivelyremove impurities including an acid soluble material, which is often anacid soluble metal oxide, such as CeO₂, Fe₂O₃, Fe₃O₄, SnO₂, Cr₂O₃, andthe like.

The present embodiment can effectively remove impurities on a surface ofa group III nitride crystal in a case where the step of polishing with aslurry is performed such that abrasive grains containing such a basesoluble material as described above and abrasive grains containing suchan acid soluble material as described above are used and a case wherethe step of polishing with a slurry is performed such that abrasivegrains containing such a base soluble material as described above andsuch an acid soluble material as described above are used.

In the present embodiment, in particular, polishing with the basicpolishing liquid and thereafter polishing with the acidic polishingliquid can particularly effectively remove impurities including such anacid soluble material as described above.

Third Embodiment

The present invention provides the method of processing a surface of agroup III nitride crystal in another embodiment with reference to FIGS.1 and 2 including the step of polishing a surface of group III nitridecrystal 1 with polishing liquid 27 at least once after polishing thesurface with polishing slurry 17 containing abrasive grains 16, and thestep of polishing with polishing liquid 27 includes the step ofpolishing with an acidic polishing liquid and polishing with a basicpolishing liquid. Herein the acidic and basic polishing liquids arethose described in the first embodiment.

Polishing with the acidic polishing liquid can effectively removeimpurities including an acid soluble material such as CeO₂, Fe₂O₃,Fe₃O₄, SnO₂, Cr₂O₃ and the like, and polishing with the basic polishingliquid can effectively remove impurities including a base solublematerial such as SiO₂, Al₂O₃, and the like.

The present embodiment can effectively remove impurities on a surface ofa group III nitride crystal in a case where the step of polishing with aslurry is performed such that abrasive grains containing such a basesoluble material as described above and abrasive grains containing suchan acid soluble material as described above are used and a case wherethe step of polishing with a slurry is performed such that abrasivegrains containing such a base soluble material as described above andsuch an acid soluble material as described above are used.

In the present embodiment, in particular, polishing with the acidicpolishing liquid and thereafter polishing with the basic polishingliquid can particularly effectively remove impurities including SiO₂ ora similar, non-metallic material or Al₂O₃ or a similar material.

Fourth Embodiment

The present embodiment provides a group III nitride crystal substrate,which is obtained by the method of processing a surface of a group IIInitride crystal, as described in the first to third embodiments. Thepresent embodiment can provide a group III nitride crystal substratehaving a surface with less impurities remaining thereon, since it isprocessed by a method, as has been described in the first to thirdembodiments, including the step of polishing the surface of the groupIII nitride crystal with a polishing liquid at least once afterpolishing it with a polishing slurry containing abrasive grains, andeach step of polishing with the polishing liquid employs the abovedescribed basic or acidic polishing liquid as the polishing liquid.

When the group III nitride crystal substrate, such as a GaN substrate,thus obtained is employed to epitaxially grow a group III nitridecrystal layer, such as In_(1-x)Ga_(x)N layer, thereon, wherein 0≦x≦1,their interface can have a reduced impurity concentration. Employing thegroup III nitride crystal substrate and layer to fabricate an LED allowsthe LED to have a less varying operating current and achieve increasedemission intensity. Furthermore, employing the above described group IIInitride crystal substrate and layer to fabricate an electronic devicecan contribute to a reduced amount of current leakage.

EXAMPLES

Hereinafter the present method of processing a surface of a group IIInitride crystal and the present group III nitride crystal substrateobtained thereby will specifically be described with reference to thefollowing comparative examples and present examples.

First Comparative Example

On an underlying substrate implemented by a sapphire substrate a GaNcrystal was grown by hydride vapor phase epitaxy (HYPE) to have athickness of 1 mm. The GaN crystal had a perimeter ground and thusbeveled. Subsequently it was sliced with a slicer having an innerperipheral edge and had a surface ground to provide a GaN crystalsubstrate having a thickness of 0.5 mm.

With reference to FIG. 1, the GaN crystal substrate (or group IIInitride crystal 1) had a surface polished with polishing slurry 17 whichcontains abrasive grains of SiO₂ having an average grain size of 0.05 μmand has a pH of 3.3 and an ORP of 1,100 mV. Polishing pad 18 wasimplemented by a polyurethane suede pad (Supreme RN-R produced by NittaHaas Incorporated) and surface plate 15 was implemented by a stainlesssteel surface plate. The surface was polished for 60 minutes such that apolishing pressure of 19.6 kPa (or 200 gf/cm²) to 98 kPa (or 1,000gf/cm²) was applied and the GaN crystal substrate (or group III nitridecrystal 1) and surface plate 15 were rotated 30 to 120 times/min.

The GaN crystal substrate was then immersed in pure water and anultrasonic wave of 1 MHz was applied to the pure water to wash a surfaceof the GaN crystal substrate for 20 minutes. Then, total reflection xray fluorescence (TXRF) was employed to provide an element analysis ofimpurity remaining on the surface of the GaN crystal substrate havingbeen washed with the pure water. 5×10¹² Si atoms/cm² were detected.

First Example

With reference to FIG. 2, the GaN crystal substrate of the firstcomparative example was polished with basic polishing liquid 27 of anaqueous solution containing 0.1 mol/l of tetra methyl ammonium oxide and0.05 mol/l of hydrogen peroxide and having a pH of 12 and an ORP of 800mV. Polishing pad 28 was implemented by a polyurethane suede pad(Supreme RN-R produced by Nitta Haas Incorporated) and surface plate 25was implemented by a stainless steel surface plate. The substrate waspolished for 20 minutes such that a polishing pressure of 19.6 kPa (or200 gf/cm²) to 49 kPa (or 500 gf/cm²) was applied and the GaN crystalsubstrate (or group III nitride crystal 1) and surface plate 25 wererotated 30 to 120 times/min. Then, similarly as has been described inthe first comparative example, the GaN crystal substrate had its surfacewashed with pure water. The GaN crystal substrate washed with pure waterwas examined for impurity remaining on the surface. 1×10¹¹ Si atoms/cm²were detected. Polishing with the basic polishing liquid, as describedin the present example, has reduced significantly more of impurityremaining on the surface of the GaN crystal substrate than the firstcomparative example.

Second Comparative Example

On an underlying substrate implemented by a ZnO substrate a GaN crystalwas grown by hydride vapor phase epitaxy (HVPE) to have a thickness of0.6 mm. The ZnO substrate was chemically etched away to obtain a GaNcrystal substrate. The GaN crystal substrate had a perimeter ground andthus beveled and then had a surface lapped with abrasive diamond grainsand etched with 0.5 mol/l of an aqueous solution of KOH to obtain a GaNcrystal substrate having a thickness of 0.45 mm.

With reference to FIG. 1, the GaN crystal substrate (or group IIInitride crystal 1) had a surface polished with polishing slurry 17 whichcontains abrasive grains of Cr₂O₃ having an average grain size of 0.3 μmand has a pH of 2 and an ORP of 800 mV. Polishing pad 18 was implementedby a polyurethane suede pad (Supreme RN-R produced by Nitta HaasIncorporated) and surface plate 15 was implemented by a stainless steelsurface plate. The surface was polished for 60 minutes such that apolishing pressure of 19.6 kPa (or 200 gf/cm²) to 98 kPa (or 1,000gf/cm²) was applied and the GaN crystal substrate (or group III nitridecrystal 1) and surface plate 15 were rotated 30 to 120 times/min.

Then, similarly as has been described in the first comparative example,the GaN crystal had its surface washed. The GaN crystal substrate washedwith pure water was examined for impurity remaining on the surface.1×10¹³ Cr atoms/cm² were detected.

Second Example

With reference to FIG. 2, the GaN crystal substrate of the secondcomparative example was polished with acidic polishing liquid 27 of anaqueous solution containing 0.1 mol/l of citric acid and 0.1 mol/l ofhydrogen peroxide and having a pH of 3.5 and an ORP of 700 mV. Polishingpad 28 was implemented by a polyurethane suede pad (Supreme RN-Rproduced by Nitta Haas Incorporated) and surface plate 25 wasimplemented by a stainless steel surface plate. The substrate waspolished for 20 minutes such that a polishing pressure of 19.6 kPa (or200 gf/cm²) to 49 kPa (or 500 gf/cm²) was applied and the GaN crystalsubstrate (or group III nitride crystal 1) and surface plate 25 wererotated 30 to 120 times/min. Then, similarly as has been described inthe first comparative example, the GaN crystal substrate had its surfacewashed with pure water. The GaN crystal substrate washed with pure waterwas examined for impurity remaining on the surface. 1×10¹⁰ Cr atoms/cm²were detected. Polishing with the acidic polishing liquid, as describedin the present example, has reduced significantly more of impurityremaining on the surface of the GaN crystal substrate than the secondcomparative example.

Third Comparative Example

On an underlying substrate implemented by a GaAs substrate a GaN crystalwas grown by hydride vapor phase epitaxy (HVPE) to have a thickness of 3mm. The GaAs substrate was chemically etched away to obtain a GaNcrystal substrate. The GaN crystal was sliced with a wire saw and thenhad a surface dry etched to obtain a GaN crystal substrate having athickness of 0.5 mm.

With reference to FIG. 1, the GaN crystal substrate (or group IIInitride crystal 1) had a surface polished with polishing slurry 17 whichcontains abrasive grains of Fe₂O₃ having an average grain size of 0.3 μmand has a pH of 2 and an ORP of 800 mV. Polishing pad 18 was implementedby a polyurethane suede pad (Supreme RN-R produced by Nitta HaasIncorporated) and surface plate 15 was implemented by a stainless steelsurface plate. The surface was polished for 60 minutes such that apolishing pressure of 19.6 kPa (or 200 gf/cm²) to 98 kPa (or 1,000gf/cm²) was applied and the GaN crystal substrate (or group III nitridecrystal 1) and surface plate 15 were rotated 30 to 120 times/min.

Then, similarly as has been described in the first comparative example,the GaN crystal had its surface washed. The GaN crystal substrate washedwith pure water was examined for impurity remaining on the surface.1×10¹² Fe atoms/cm² were detected.

Third Example

With reference to FIG. 2, the GaN crystal substrate of the thirdcomparative example was polished with basic polishing liquid 27 of anaqueous solution containing 0.1 mol/l of tri methyl ammonium oxide and0.1 mol/l of hydrogen peroxide and having a pH of 11 and an ORP of 500mV. Polishing pad 28 was implemented by a polyurethane suede pad(Supreme RN-R produced by Nitta Haas Incorporated) and surface plate 25was implemented by a stainless steel surface plate. The substrate waspolished for 20 minutes such that a polishing pressure of 19.6 kPa (or200 gf/cm²) to 49 kPa (or 500 gf/cm²) was applied and the GaN crystalsubstrate (or group III nitride crystal 1) and surface plate 25 wererotated 30 to 120 times/min. Then, similarly as has been described inthe first comparative example, the GaN crystal substrate had its surfacewashed with pure water. The GaN crystal substrate washed with pure waterwas examined for impurity remaining on the surface. 1×10¹¹ Fe atoms/cm²were detected. Polishing with the basic polishing liquid, as describedin the present example, has reduced significantly more of impurityremaining on the surface of the GaN crystal substrate than the thirdcomparative example.

Fourth Example

With reference to FIG. 2, the GaN crystal substrate of the third examplewas polished with acidic polishing liquid 27 of an aqueous solutioncontaining 0.1 mol/l of malic acid and 0.1 mol/l of hydrogen peroxideand having a pH of 2.5 and an ORP of 1,000 mV. Polishing pad 28 wasimplemented by a polyurethane suede pad (Supreme RN-R produced by NittaHaas Incorporated) and surface plate 25 was implemented by a stainlesssteel surface plate. The substrate was polished for 20 minutes such thata polishing pressure of 19.6 kPa (or 200 gf/cm²) to 49 kPa (or 500gf/cm²) was applied and the GaN crystal substrate (or group III nitridecrystal 1) and surface plate 25 were rotated 30 to 120 times/min. Then,similarly as has been described in the first comparative example, theGaN crystal substrate had its surface washed with pure water. The GaNcrystal substrate washed with pure water was examined for impurityremaining on the surface. 1×10¹⁰ Fe atoms/cm² were detected. Polishingwith the acidic polishing liquid, as described in the present example,has reduced significantly more of impurity remaining on the surface ofthe GaN crystal substrate than the third comparative example and thethird present example.

Fourth Comparative Example

On an underlying substrate implemented by a sapphire substrate a GaNcrystal was grown by organometallic vapor phase epitaxy (OMPVE) to havea thickness of 0.3 mm. That side of the sapphire substrate which isopposite to the GaN crystal was exposed to laser light to separate theGaN crystal from the sapphire substrate to obtain a GaN crystalsubstrate. The GaN crystal substrate then had a perimeter ground andthus beveled and was then etched with an aqueous solution containing 0.1mol/l of choline to obtain a GaN crystal substrate having a thickness of0.35 mm.

With reference to FIG. 1, the GaN crystal substrate (or group IIInitride crystal 1) had a surface polished with polishing slurry 17 whichcontains abrasive grains of SnO₂ having an average grain size of 3 μmand has a pH of 3 and an ORP of 700 mV. Polishing pad 18 was implementedby a polyurethane suede pad (Supreme RN-R produced by Nitta HaasIncorporated) and surface plate 15 was implemented by a stainless steelsurface plate. The surface was polished for 60 minutes such that apolishing pressure of 19.6 kPa (or 200 gf/cm²) to 98 kPa (or 1,000gf/cm²) was applied and the GaN crystal substrate (or group III nitridecrystal 1) and surface plate 15 were rotated 30 to 120 times/min.

Then, similarly as has been described in the first comparative example,the GaN crystal had its surface washed. The GaN crystal substrate washedwith pure water was examined for impurity remaining on the surface.1×10¹³ Sn atoms/cm², 1×10¹² Cu atoms/cm² and 1×10¹² Zn atoms/cm² weredetected.

Fifth Example

With reference to FIG. 2, the GaN crystal substrate of the fourthcomparative example was polished with basic polishing liquid 27 of anaqueous solution which contains 0.3 mol/l of ammonium, 0.1 mol/l ofhydrogen peroxide and a chelate implemented by 0.1 mol/l of EDTA, andhas a pH of 11 and an ORP of 500 mV. Polishing pad 28 was implemented bya polyurethane suede pad (Supreme RN-R produced by Nitta HaasIncorporated) and surface plate 25 was implemented by a stainless steelsurface plate. The substrate was polished for 20 minutes such that apolishing pressure of 19.6 kPa (or 200 gf/cm²) to 49 kPa (or 500 gf/cm²)was applied and the GaN crystal substrate (or group III nitride crystal1) and surface plate 25 were rotated 30 to 120 times/min. Then,similarly as has been described in the first comparative example, theGaN crystal substrate had its surface washed with pure water. The GaNcrystal substrate washed with pure water was examined for impurityremaining on the surface. 3×10¹⁰ Sn atoms/cm², 5×10¹⁰ Cu atoms/cm² and5×10¹⁰ Zn atoms/cm² were detected. Polishing with a basic polishingliquid containing a chelate, as described in the present example, hassignificantly reduced impurities, such as Sn, Cu, Zn and the like,remaining on the surface of the GaN crystal substrate.

Fifth Comparative Example

Similarly as has described in the first comparative example, a GaNcrystal substrate of 0.5 mm in thickness was obtained. With reference toFIG. 1, the GaN crystal substrate (or group III nitride crystal 1) had asurface polished with polishing slurry 17 which contains abrasive grainsof SiO₂ having an average grain size of 0.1 and abrasive grains of Cr₂O₃having an average grain size of 0.3 μm and has a pH of 2.5 and an ORP of1,100 mV. Polishing pad 18 was implemented by a polyurethane suede pad(Supreme RN-R produced by Nitta Haas Incorporated) and surface plate 15was implemented by a stainless steel surface plate. The surface waspolished for 60 minutes such that a polishing pressure of 19.6 kPa (or200 gf/cm²) to 98 kPa (or 1,000 gf/cm²) was applied and the GaN crystalsubstrate (or group III nitride crystal 1) and surface plate 15 wererotated 30 to 120 times/min.

Then, similarly as has been described in the first comparative example,the GaN crystal had its surface washed with pure water. The GaN crystalsubstrate washed with pure water was examined for impurity remaining onthe surface. 5×10¹² Si atoms/cm² and 1×10¹² Cr atoms/cm² were detected.

Sixth Example

With reference to FIG. 2, the GaN crystal substrate of the fifthcomparative example was polished with basic polishing liquid 27 of anaqueous solution containing 0.1 mol/l of choline and 0.05 mol/l ofhydrogen peroxide and having a pH of 12 and an ORP of 800 mV. Polishingpad 28 was implemented by a polyurethane suede pad (Supreme RN-Rproduced by Nitta Haas Incorporated) and surface plate 25 wasimplemented by a stainless steel surface plate. The substrate waspolished for 20 minutes such that a polishing pressure of 19.6 kPa (or200 gf/cm²) to 49 kPa (or 500 gf/cm²) was applied and the GaN crystalsubstrate (or group III nitride crystal 1) and surface plate 25 wererotated 30 to 120 times/min.

Then, the GaN crystal substrate having been polished with the basicpolishing liquid was, again with reference to FIG. 2, polished withacidic polishing liquid 27 of an aqueous solution containing 0.05 mol/lof hydrochloric acid and 0.1 mol/l of hydrogen peroxide and having a pHof 3 and an ORP of 700 mV. Polishing pad 28 was implemented by apolyurethane suede pad (Supreme RN-R produced by Nitta HaasIncorporated) and surface plate 25 was implemented by a stainless steelsurface plate. The substrate was polished for 20 minutes such that apolishing pressure of 19.6 kPa (or 200 gf/cm²) to 49 kPa (or 500 gf/cm²)was applied and the GaN crystal substrate (or group III nitride crystal1) and surface plate 25 were rotated 30 to 120 times/min.

Then, similarly as has been described in the first comparative example,the GaN crystal substrate had its surface washed with pure water. TheGaN crystal substrate washed with pure water was examined for impurityremaining on the surface. 1×10¹¹ Si atoms/cm² and 1×10¹⁰ Cr atoms/cm²were detected. Polishing with an alkaline polishing liquid and polishingwith an acidic polishing liquid, as described in the present example,has reduced significantly more of impurity remaining on the surface ofthe GaN crystal substrate than the fifth comparative example.

In the fifth comparative example and the present example, in particular,the step of polishing with a polishing slurry containing their abrasivegrains is performed such that abrasive grains of SiO₂ and those of Cr₂O₃smaller and larger, respectively, in hardness than the group III nitridecrystal are used to allow the crystal to have a surface enhanced insmoothness and to allow the surface to be polished faster. Furthermore,the abrasive grains of SiO₂ are formed of SiO₂, which is a base solublematerial, and the abrasive grains of Cr₂O₃ are formed of Cr₂O₃, which isan acid soluble material. Thus the group III crystal substrate having asurface polished with polishing slurries containing abrasive grains of abase soluble material such as SiO₂ and those of an acid soluble materialsuch as Cr₂O₃, respectively, can be polished with an alkaline polishingliquid and an acidic polishing liquid to reduce impurities deriving fromboth types of abrasive grains.

Although the present invention has been described and illustrated indetail, it is clearly understood that the same is by way of illustrationand example only and is not to be taken by way of limitation, the spiritand scope of the present invention being limited only by the terms ofthe appended claims.

1-5. (canceled)
 6. A method of processing a surface of a group IIInitride crystal, the method comprising the steps of: polishing a surfaceof a group III nitride crystal with a polishing slurry containingabrasive grains; and thereafter polishing said surface of said group IIInitride crystal with a polishing liquid that does not contain abrasivegrains at least once, wherein: each step of polishing with saidpolishing liquid employs one of a basic polishing liquid and an acidicpolishing liquid as said polishing liquid; and said basic polishingliquid contains at least one type selected from the group consisting ofa base having at least any of C, O, H and N as a constituent element, asalt thereof and an oxidizer and has a pH of at least 8.5 and at most14, and if said pH is represented by a value x and said basic polishingliquid has an oxidation reduction potential represented by a value yrepresented in mV, said values x and y satisfy the following expression:y>−50x+800  (i); said acidic polishing liquid contains at least one typeselected from the group consisting of an acid having at least any of C,O, H and N as a constituent element, a salt thereof and an oxidizer andhas a pH of at least 1.5 and at most 6, and if said pH is represented bya value x and said acidic polishing liquid has an oxidation reductionpotential represented by a value y represented in mV, said values x andy satisfy the following expression:y>−50x+800  (i).
 7. The method of processing a surface of a group IIInitride crystal according to claim 6, wherein said basic polishingliquid further contains a chelate.
 8. The method of processing a surfaceof a group III nitride crystal according to claim 6, wherein said stepsof polishing with said polishing liquid include the steps of polishingwith said basic polishing liquid and thereafter polishing with saidacidic polishing liquid.
 9. The method of processing a surface of agroup III nitride crystal according to claim 6, wherein said steps ofpolishing with said polishing liquid include the steps of polishing withsaid acidic polishing liquid and thereafter polishing with said basicpolishing liquid.
 10. A group III nitride crystal substrate obtained bya process for processing a surface of a group III nitride crystal,wherein: said process includes the steps of: polishing a surface of agroup III nitride crystal with a polishing slurry containing abrasivegrains; and thereafter polishing said surface of said group III nitridecrystal with a polishing liquid that does not contain abrasive grains atleast once; each step of polishing with said polishing liquid employsone of a basic polishing liquid and an acidic polishing liquid as saidpolishing liquid; and said basic polishing liquid contains at least onetype selected from the group consisting of a base having at least any ofC, O, H and N as a constituent element, a salt thereof and an oxidizerand has a pH of at least 8.5 and at most 14, and if said pH isrepresented by a value x and said basic polishing liquid has anoxidation reduction potential represented by a value y represented inmV, said values x and y satisfy the following expression:y>−50x+800  (i); said acidic polishing liquid contains at least one typeselected from the group consisting of an acid having at least any of C,O, H and N as a constituent element, a salt thereof and an oxidizer andhas a pH of at least 1.5 and at most 6, and if said pH is represented bya value x and said acidic polishing liquid has an oxidation reductionpotential represented by a value y in represented mV, said values x andy satisfy the following expression:y>−50x+800  (i).